Certain polyepoxide treated derivatives of monoepoxide-amine modified-resins, and method of making same



hydrin and subsequently with an alkali.

United Sttes Patent CERTAIN POLYEPOXIDE TREATED DERIVATIVES OF MONOEPOXIDE-AMINE MODIFIED-RESINS, AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, and Kwau-Ting Shen, Brentwood, 'Mo., assignors to 'Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application June 10, 1953, Serial No. 360,842, new Patent No. 2,792,361, dated May 14, 1957. Divided and this application September 11, 1956, Serial No. 609,092

12 Claims. (Cl. 260-43) or compounds in various other arts and industries as well as with methods of manufacturing the new chemical prod ucts or compounds which are of outstanding value in demulsification.

The present invention is concerned with a 3-step manufacturing process involving (1) condensing certain phenol aldehyde resins, hereinafter described in detail, with certain basic hydroxylated secondarymonoamines, hereinafter described in detail, and formaldehyde; (2) oxyalkylation of the condensation product with certain monoepoxides, hereinafter described in detail; and (3) oxyalkylation of the previously oxyalkylated resin condensate with certain non-aryl polyepoxides, also hereinafter described in detail.

The present invention is characterized by the use of compounds derived from diglycidyl ethers which do; not introduce any hydrophobe properties in its usual meaning but in fact are more apt to introduce hydrophile properties. Thus, the diepoxides employed in the present invention are characterized by the fact that the divalent radical connecting the terminal epoxide radicals contains less than 5 carbon atoms in an uninterrupted chain.

The diepoxides employed in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending application, Serial No. 350,532, are invariably and inevitably aryl in character.

The diepoxides employed in the present process are usually obtained by reacting a glycol or equivalent compound, such as glycerol or diglycerol, with epichloro- Such diepoxides have been described in the literature and particularly the patent literature.

Reference to being thermoplastic characterizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to .rings.

ice

solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubilityis a factor insofar that it sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an .oxyalkylated amine condensate. In such instances, of course, thesolvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene, dioxane, possibly various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether,.and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is-sometimes referred to as the oxirane ring to distinguish it from other epoxy Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound hastwo or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxy rings or oxirane rings in the alpha-omega position. This is a departurefrom the standpoint of strictly formal nomenclature as in the exampleof the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane(1,2,3,4 diepoxybutane).

It well may be that even though the previously suggested formularepresents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric compounds containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included arerlimited tothe monomers or the low molal members ofrsuch series and generally contain two epoxide rings per molecule'and'may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Simply for purpose of illustration to show a typical diglycidyl ether of the kind herein employed reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

H H HC-O-OH H H H l H H H HG-C-G-O H HCOOHCOH H Ho-o-oH H H or the equivalent compound wherein the ring structure involves only 6 atoms, thus:

a H H|0CH Hc-o-cH l Commercially available compounds seem to be largely the former with comparatively small amounts, in fact, comparatively minor amounts, of the latter.

Having obtained an acyclic reactant having generally 2 epoxy rings as depicted in the next to last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any oxyalkylated phenol-aldehyde resin condensate by virtue of the ,fact

that there are always present either phenolic hydroxyl radicals or alkanol radicals resulting from the oxyalkylation of the phenolic hydroxyl radicals; there may be I reacted with a product having both a nitrogen group and present reactive hydrogen atoms attachedto a nitrogen atom or an oxygen atom, depending on whether initially there was present a hydroxylated group attached to an amino hydrogen group or a secondary amino group. In any event there is always a multiplicity of reactive hydrogen atoms present in the oxyalkylated amine-modified phenol-aldehyde resin.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having 2 oxirane rings and an oxyalkylated amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of 2 moles of the oxyalkylated amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

in which n is a small whole number less than 10, and

usually less than 4, and including 0, and R represents a.

containing an acid such as hydrochloric acid, acetic acid,

hydroxyacetic -acid,etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride,.etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their Weight of 5% gluconic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for

instance, 80 parts of xylene and 20 parts of methanol,

or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone. .As oxyalkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

The polyepoxide-treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and valuable derivatives can be obtained by further. reaction with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as Wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road build ing and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade Wastes and the like; as germicides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufficiently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as'such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product i being examined and then mix with the equal weight of .xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience, what is said hereinafter will be divided into eight parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides and particularly diepoxides employed as reactants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield an amine-modified resin;

Part 3 is concerned with appropriate basic hydroxylated secondary monoamines which may be employed in the preparation of the hereindescribed amine-modified resins;

Part 4 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products orcompounds which are then subjected to oxyalkylation with monoepoxides;

Part 5 is concerned with the oxyalkylation of the ,products described in Part 4, preceding;

a polyepoxide 1 so as to yield a newand larger resin molecule or comparable product Part-7 is concerned withthe resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 8 is concerned with uses for theproductsherein; describedeither as such or-after modification, including any'applicationsother than those involvingresolutionjof petroleum emulsions of the water-in-oil type.

PART- 1 Reference is made to various patents as illustrated in the manufacture of the nonaryl polyepoxides and particularly diepoxides employed as reactants in the instant invention. More'specifically, such patents are the following: Italian Patent No. 400,973, dated August 8, 1941; British Patent No. 518,057, dated December 10, 1938; U. S. Patent No..2,0 70,990, dated February 16, 1937 to Groll et al; and U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl ethers may be indicated thus:

dated February 16, 1937, to Groll, and is of the following formula H2C/\CCH2CH2C/.-\CH2 CH3 CH3 The diepoxides previously described may beindicated by the following formula:

H R R H HC" C[R ]n O 'CH in which R represents a hydrogen atom or methyl radical and R represents the divalent radical uniting the two terminal epoxide groups, and n is the numeral 0 or 1. As previously pointed out, in the case of the butadiene derivative, n is 0. In this case of diisobutenyl dioxide R is CH --CH and n is 1. In another example previously referred to R is CH OCH and n is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equiv-- alent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycerols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case,

'6 methyl epichlorohydrin. So presentedthe formula. becomes:

11- H H H H 11-. HC O,-C-o['R1iO CC -CH H H In the above formula R is selected from groups such as the following:

is derived actually or theoretically, or at least derivable, from the diol HOROH, in'which the oxygen-linked hydrogen atoms were-replaced by t CO+OH Thus, R(OH),,, where n represents a small whole number which is 2 or more, must be water-soluble. Such limitation excludes polyepoxides if actually derived or theoretically derived at least, from water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms, orv thereabouts.

Referring to a compound of the type above in the formula in which R is C H (OH) it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R' happened to be C H (OH)OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides arealso present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately .4. moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular weight is approximately 370 and the number of epoxide groups per molecule are approximately 2. For this reason in the first of a senesof subsequent examples this particular diglycidyl ether is used, although obviously any of the others previously de-.

scribed Wouldbe just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such 7 material corresponds in a general way to the previous formula. 7

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds is to use the terminology epoxyalkanes, and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom, and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal class properly may be referred to as polyepoxy polyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

PART 2 R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance, paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. ample 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to -De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all See Exthat is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble. as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylationsusceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resins, having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity, are derived by reaction be tween a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described pre viously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic hydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R\ H OHHl'OHH-I OHH /R' N-o -0 0 C-N H H H H R R! R R R The basic hydrox'ylated amine may be designed thus:

RI HN -In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

0 H O H I O H O IH U IH O R R. n R

in which- R"" is the divalent: radical obtained from the particular aldehyde employed to form. the resin. For reasons which are obvious thecondensation product obtained appears to be described best in terms of the method of manufacture.

As. previously stated the preparation of resins, the kind herein employed as. reactants, is well known. See previously mentioned U'. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalysthaving neither acid: nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed. be. substantially neutral. Inother words, if prepared by using a strong acid asa catalyst such strong acid. should be neutralized. Similarly, if a. strong base is. used as a catalyst it is preferable that thebase be neutralized'although we have found that sometimes. thereaction described proceeded more-rapidly in thepresence of a small amount of a free base. The amount may be.as small as a: 200tl1of a; percent and as much as a few 10ths of a, percent; Some,- times moderate increase. in caustic; soda and. caustic potash may be used. However, the most desirable procedurein practically every. case, is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having. just 3 units, or just 4 units, or just- 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approximately 4 phenolic nuclei will have some trimer and; pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture. of the resins we found no reason. for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

Table I M01. wt.

Ex- Position R of resin ample R of R derived n molecule number trom-- (based on n+2) Tertiary butyl Para Formal- 3.5 882. 5

Secondary butyl. Ortho 3. 5 882. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3; 5 805. 5

and tertiary amyl;

3. 5 805. 5 3. 5 1, 036.5 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 yl 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl 3. 5 1, 022. 5 Nonyl M 3. 5 1, 330.- 5 Tertiary butyl 3. 5 1, 071.5

Tertiary arnyl do do 3. 5 1, 148. 5 Nonyl do do 3. s 1,456.5 Tertiary butyl do. Propional- 3. 5 1, 008.5

' dehyde.

Tertiary amyl. 3. 5 1,085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl 4. 2 996. 6

Tertiary amyl 4.2 1, 08 3. 4 No 4.2 1, 430. 6 4. 8 1, 094. 4 4. 8 1, 189. 6 4. s 1, 570. 4 1.5 604.0 1. 5 653.0 1. 5 688.0

As has been pointed out previously the amine herein employed as. a reactant is. a basic hydroxylated" secondary monoamine. whosel composition is indicated. thus:

in which R represents a monovalentalkyl, alicyclic, arylalkyl radical which may be heterocyclic in a few instances as in a secondary: amine derived from furfurylamine by reaction of ethylene oxide or propylene oxide. Furthermore, at least one of the radicals designated by R' must have at least one hydroxyl radical. A large number of secondary amines are available, and may be suitably employed as reactants for the present purpose. Among others, one may employ diethanolamine, methyl ethanolamine, dipropanolamine andethylpropanolamine. Other suitable secondary amines are obtained, of course, by taking any suitable primary amine, such as an alkylamine, an arylalkylamine, or an alicyclic amine, and treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylamine, 'amylamine, hexylamine, higher molecular weightamines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc. In other instances'secondary amines which have at least one hydroxyl radical can be treated similarly with an oxyalkylating agent, or, for that matter, with an alkylating agent such as benzylchloride, esters ofchloroacetic acid, al'kyl' bromides, dimethylsulfate, esters of sulfonic acid, etc., so as to convert the primary amine into a secondary amine. Among others, such amines include 2-amino-1-butanol, 2 amino 2- methyl 1 propanol, Z-amino-Z-methyl- 1 3 propanediol, 2 amino 2-ethyl-1,3-propanedi'o1, and tri(hydroxymethyl) -aminomethane. Another example of such amines is illustrated by 4-amino-4- IiQthyl- Z-pentanol.

Similarly, one can prepare suitable secondary amines which have not only a hydroxyl group but also one or more divalent oxygen linkages as part of an ether radical. Examples included are:

(0 11110 CzH4O 6211 002114) 110021314 (C4H9O CH2CH(CH3) 0 (CH3) CECE!) HOCZHA/ (CHaO QHzCHzO CHaCHzO CH2C 2).

/NH HOCZHA (CHQO CHzCHzCHtCHzCHzCHt) HOC2H4 or comparable compounds having two hydroxylated.

groups of diiferent lengths as in (H0 CHzCHzO CHzCHzO CHzCHr) no CgHt Other examples of suitable amines include alpha-methylbenzylamine and monoethanolamine; also amines obtained by treating cyclohexylmethylamine with one mole of an oxyalkylating agent as previously described; beta ethylhexyl-butanolamine, diglycerylamine, etc. Another type of amines which is of particular interest because it includes a very definite hydrophile group includes sugar amines such as' glucamine, galactamine and fructamine, such as N-hydroxyethylglucamine, N-hydroxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by CH! CHsl LCiEfiOH I'm CHLJLCHrOH 1H;

See, also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in U. S. Patent No. 2,510,063, dated June 6, 1950, to Brief. Still other examples are illustrated by treatment of certain secondary amines, such as the following, with a mole of an oxyalkylating agent as described; phenoxethylamine, phenoxypropylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxyl group and a single basic amino nitrogen atom can be obtained from any suitable alcohol or the like by reaction with a reagent which contains an epoxide group and a secondary amine group. Such reactants are described, for example, in U. S. Patents Nos. 1,977,251 and 1,977,253, both dated October 16, 1934, to Stallmann. Among the reactants described in said latter patent are the following:

PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction it employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at'l50' C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such orsimilar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohols should not be used or else they should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

The products obtained, depending on the reactants selected, may be water-insoluble, or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There even desirable to hold the low temperature stage formore than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature, then the amount of unreacted formal dehyde is decreased subsequently and makes it easier tof prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previ-;

ously referred to.

If solvents and reactants are selected so the reactants; and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the a selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely dissolved. However, if the resin is prepared as such it may beadded in solution form, just as preparation is described in aforementioned U. S. Patent' 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a threephase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example, 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of amine or formaldehyde. At a higher temperature we use a phaseseparating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C., by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surfaceactivity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation prod ucts. The following example will serve by way of illustration.

Example 1b The phenol-'aldehyderesin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. Thiscorresponded to anaverage of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with 700 grams of xylene. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 210 grams of diethanolamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde used was a 37% solution and 160 grams were employed which were added in about 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 21 hours. At the end of this period of time it was refluxed, using a phase separating trap and a small amount of aqueous distillate withdrawn from time to time and the presence of un reacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within approximately 3 hours after the refluxing. was started. As soon as the odor of formaldehyde was no longer detectible the phaseseparating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached about 150 C. The mass was kept at this higher temperature for about 3% hours and reaction stopped. During this time any additional water, which was prob ably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the.

. fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solu tion and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to C. or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II. V

Table II Strength of Reac- Reac- Max. Ex. Resin Amt, formal- Solvent used tion tlon dis- N 0. used grs. Amine used and amount dehyde and amt. temp., time till.

soln. and 0. (hrs.) tern amt.

882 Diethanolaminc, 210 g- 37%, 162 g... Xylene, 700 g. 22-26 32 137 480 Diethanolemine, 105 g 37%, 81 g Xylene, 450 g 21-23 28 150 d Xylene, 600 g 20-22 36 145 Xylene, 400 g 20-23 34 146 Xylene, 450 g 21-23 24 141 Xylene, 600 g 21-28 24 145 Xylene, 700 g 20-26 24 152 Xylene, 450 g 24-30 28 151 Xylene, 600 g 22-25 27 147 Xylene, 450 g 21-31 31 146 .do 22-23 36 148 Xylene, 550 g 20-24 27 152 181). 2a.- Xylene, 400 g 21-25 24 160 HOCzH CIHlO CIHIOOIH 14b a....- 480 H, 176 g do..... Xylene, 450 g 20-26 26 146 HOCIH C1H OCgHO CzHA b 9a- 595 NH, 176 g do.-.-.- Xylene, 550 g 21-27 30 147 HOOIH| HOCIHOCIHOCIHL 166--.- 2a.- 441 NH, 192 g u. .-do Xylene, 400 g -22 30 148 HOCzH HOCIBQO CjHIOCIHl 175--.- 5a- 480 r H, 192 g.--- dn dn 20-25 28 150 HOCIHA HO CzHrO CzHAO 02H;

185--.. 142-.-. 511 H, 192 g do- Xylene, 500 g 21-24 32 149 HOCzHi HOC2HAOCIH4OCZHA 19b- 220-..- 498 192 g do Xylene, 450 g 22-25 32 153 HOOzH O a(0C2 1)! 200.-.- 230."- 542 H, 206 g 30%, 100 g Xylene, 500 g 21-23 36 151 V CH2( 2 0a 21b-.- a.. 547 NH, 206 g --.do "do"; 25-30 34 148 HOO H;

CH;(O 02H)! 2a... '441 NH, 206 g d.o Xylene, 400 g... 22-23 31 146 595 Decylethanolamme, 201 37%, 81 g Xylene, 500 g. 22-27 24 145 391 Decylethanolamine, 100 g..- g Xylene, 300 g 21-25 26 147 PART 5 Example 10 The oxyalkylation-susceptible compound employed is the one previously described and designated as Example lb. Condensate 1b was in turn obtained from diethanolamine and the resin previously identified as Example 2a. Reference to Table I shows that this particular resin is obtained from para-tertiarybutylphenol and formaldehyde. 11.16 pounds of this resin condensate were dissolved in 7 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately C. to C., and at a pressure of about 15 to 20 pounds.

The time regulatorwas set so as to inject the ethylene oxide in approximately two hours and then continue stirring for a half-hour or longer. The reastion went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. More specifically it was complete in 45 minutes. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 11.16 pounds. This represented a molal ratio of 25 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2232.. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of thistact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables III an IV.

The size of the autoclave employed was 25 gallons. In

innumerable comparable 'oxyalkylations I have with drawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the ease in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 2c This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example lb, present at the beginning of the stage was obviously the same'as at the end of the prior stage (Example 1c), to wit, 11.16 pounds. The amount of oxide present in the initial step was 11.16 pounds, the'amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 11.16 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylati'on step the amount of oxide added was a total of 22.32 pounds and the molal ratio of ethylene oxide to resin condensate was 50.8 to 1 The theoretical molecular weight was 3348.

The maximum temperature during the operation was 130 C. to 135 C. The maximum pressure was in the range of 15 to 20 pounds; The time period was one hour.

Example 30 The oxyalkylation proceeded in the same manner described in Examples and 20. There was no added solvent and no added catalyst. The oxide added was 11 .16 pounds and the total oxide at the end of the oxyethylation' step was 33.48 pounds. The molal ratio of oxide to condensate was 76.2 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Examples 1 c and 2c. The time period. was somewhat longer than in previous examples, to wit, 2 hours.-

Example 4 The oxyethylation Was continued and the amount of oxide added again was 11.16 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 5580. The molal ratio of oxide to condensate was 101.6 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly'longer, to Wit, 3 /2 hours. The reaction unquestionably began to slow up somewhat.

Example 5c The oxyethylationcontinued with the introduction of another 11.16 pounds of ethylene oxide; No more-solvent was introduced but .3 pound caustic soda was added. The-theoretical molecular'weight at the end of the agitation; period was 6696. and the molal ratio of oxide to resin condensate was 127 to 1. The time period, however, dropped to 1% hours. Operating temperature and pressureremained the same as in the previous example.

examples except that an added pound of powdered caustic soda was introduced to speed up the reaction. The-amount of oxide added was another 11.16 pounds, bringing the total oxide introduced to 66.96 pounds. The

temperature and pressure during this period werethe same as before. There was no added catalyst and also no added-solvent. The time p'efio'd "2 /1 Hours.

Example 7c The same procedure was f ollowed as in theprevious six examples without the addition of more causticor more solvent. The total ain'o'tintof oxide introduced at the end or the period was 78.12- pounds; ;The theoretical molecular weightat the end of the exyaikyrstroniinu was 8928'. The time required for the-ioxyethylaition was a bit longer than in the previous step, to wit, 3 hours;

I Example This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end or this step was 89.28 pounds. The theoretical molecular weight was 10,044. The molal ratio of oxide to resin condensate was 203 .-2 to one. Conditions as far as temperature and pres; sure were concerned were the same as in the previous examples and the time required for oxyethylat'ion was 4 hours. y x

The same procedure as described in the previous amples is employed in connection witha number of the other condensates described previously; AllKthese data have been presented in tabular form in a series of four tables, Tables III and IV, V and in substantially every case a 25 -gall on autoclave was employed, although in some inst'ancesf the initial oxyetliy latiorr was started in a l5 -gallon autoclave and then transffer i ed' to a 25-gallon autoclave. This is immaterial biit happened to be arnatter of convenience only. The solvent used in all cases was xylene; The catalyst used was finely p w de led caustic soda; v

Referring now to Tables III and ob't'a'ine By the use of ethylene oxide, whereas 41c through 806 tvereets tained bythe' use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows.

The example number of each compound is indicated in the first column;

The identity of the oxyalkylation-s usceptible-compoiliidi to Wit, the resin condensate;- is" indicated iii" the second column.

The amount of condensate is shown in the thirc'lj-co'liimn. Assuming that ethylene oxide alone is employed; as happens to be the case in Example-1c through 406, the amount of oxide present in the oxyalkylation derivat as is shown in column 4', although in the initials'te'p since no oxide is present there is a blank'.

When ethylene oxide is used exclusively the Stli'cblumn is blank.'

The 6th column shows the amount of pewaered'causae soda used as a catalyst, and the 7th eoiuma shows thc amount of solvent employed: k The 15th column showsthe theoretical molecular weight at the end of the oxyalkylation'period. v

The 8th column statesthe amount ofcondensate'present in the reaction mass at the end of theperiod. U

A's p'ointed out previously, in this particular series the amount of reaction mass withdrawn for examination so small that it was ignored andfor this reason the resin condensate in column 8 coincides with the'figu'r'e' incol- Column 9 shows the amount of ethylene oxide em; ployed in'the reaction mass at the ens of the particular period.

Table III I 2 2 O0 0 2604 28 06284 42 86 da e anmmwraaomosmmommsazoanmien agli mr enm 234 6890570257021234556p 570 n 036 73 40 Oww fl 23 %5 6 7 om0 2 3 6fin aQLznmnmfiwnwn emowafiw-mkw omoLLz2&345m M m. 1 11 1.. .t 1e 0 pdw wawm. .1 oiokC t TX m m P W UC M A 4b 1 .1 0 MWYWM. M mm n E mm d t s n 6 0000000055555555000000005555555500000000 M MD 7 Z" TZZZ- A A14 dAMA4111111111111111111111111 SW1 m nu q. 0 0003333000033330000.63330000333300003333 m. mam LLLLLLLLLLLLLLLLLLLLLLL.LLLLLLLLLLLLLLLLL m W 0 C 1 ww m X Po c I 6284062 00000000 82604 2 28 062886420864 ti. 1 2 3 5 nD &9 2 o 7 0 2 5 7 U 122 iifiwzflalohniulaiLnmzlnmflmdn EM 123M5678 zsfisn sm nlaw ufi7812356H 8m 1122334 n. d 1111111155555555888 8 885555555511111111 rD LLL.LLLLLZZZZZZZZUQUOQQQQZZZZ ZZZLLLLLLLL oml 111111111 1.1111111111111111 11111111111 C 0000000055555555000000005555555500000000 mnm 111111114 1114 4 11TllZl-L- li miinmamidfiL-L-LlZ- IZ SW1 w 0000333300003333000033330000333300003333 Rm LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL V. C m m L r u e e b OHM u n Xl 0 PO i t .1 S 6284 2 2604 28 062 642086 0. b L2 3 4 56 & .2 5 7 0 2 :7 ZUHLnLQw QEW 2 5 n Z5 -L :u .L6 2 7 3 0m w u 6 66666 6 d mwwwwwmmwmmmwwmmmfififimmmmmwm%ummwwmw5mwmmlllllml b LLLl 0m 1111 c Q d wpN OmL .0 Ce 1 M X E oxyalkylation-susceptible. Column 10 can be ignored insofar that no propylene oxide was employed.

use of both ethylene oxide and propylene oxide. Since compounds 10 through c were obtained by the use of ethylene oxide, it is obvious that those obtainedfrom Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene oxide to condensate.

In the preparation of this series indicated by the small Colun1n14 can be ignored for the reason that no propylletter d, as 1d, 2d, 3d, etc., the initial 0 series such ene oxide was employed. as 350, 39c, 53, and 62c, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original perature oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be oted that the initial product, i. e., 350, consisted of the reaction product involving 11.16 pounds of the resin condensate, 16.74 pounds of ethylene oxide, 1.0 pounds of caustic soda, and 7.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. ylene Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation d, step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of These compounds involve the 7:; the next step, except obviously at the very start the value H 0 6 a a inseam m e.. a s t p n w wawmm. cm o a a O .1 f U D r. h e m. s n ad 0 m m e a i. h b .l 6 S 00 e 6 C e 3 d X t m V. e 6 Ci. 0 9. mm hfm n m w mo mmr t. t. d S 6 e O u i W f. U a 0 m m m u mu mea s e u a a mm m mm t. e m ma wr Mm mn m m m m m 1 t. rm S 6H m H 0 e H 4 U 6 m S B m n m u mmw s mm w t c .m w miwm w m ekm m m nh I 1 e M s c e S nf fm C P c d w 6 n 6 a nmmww m mmm mmnrn m 1 S a VM M .m m nmm s x m zm 0 ml n mv mw mnwum mwm nm 1 e 3 ee. m m wwmm m mmmfi? En m va nn x n 2 omm mumlhwoo Ebarm w w mnm umfm m m ward .m w @ma 0 g c m C 0 e a r 0 e e 0 S u n wfl n ce maT nd 03 f C.1 0. O mnhmm mmm mm m n r. O t mmm mnmmm w wwmm .1 S a C r. mumm mm tiwtemm nmma c .md Yn e HM Ue um a a c in h mhhm mfl mo nmdewm kuTm TTsmm mnmR w Rm m e c any Pm w m& o m m2tm3w Molee.

. wt. based oretical value The reason oxide on thetoo alkyl.

987 0013468147 76 30851356815899888665 lau-bwnoonz24 680593H35M936024680593 1234780 112 1112 112 1112 1 Molal ratio Ethyl. Propl. oxide to ex alkyl.

' susoep't; suscept.

Condensation of a' nitrogduets As far as use in demulsifica Sol. vent, 7 lbs.

'Pr o Composition at end lyst,

111114 441111155511111555222225551111144 4 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL Piopl. Cate oxide,

oxide,

Generally speaking, the amount of alkaline catalyst U48 E thl.

and"

11111111 2222 2000000002222 2211111111 111111llmmllllmlllllllllllllmm1111111111 amber tint to a definitely red, and amber. is primarily that no eflort -is made --to obtaineolorless resins initially and the resins-themselves may be yellow, amber, oreven dark amber. enous product'invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds 'no'thingto'the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product; which the final color is a lighter amber With'a reddish tint. Such products can be decolorized {b the use ofcla'y's, bleaching chars, etc.

tion is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

present is comparatively small and it need not be re moved. Since the products per so are alkaline due to the presence of a basic nitrogen atom, the" removal of the alkaline catalyst is somewhat more diificult than ordinarily is the case for the reason that if one adds hydro chloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionableor else add a stoichio metric amount of concentrated hydrochloric acid equal Table IV vent,

a a a t n 0 00000005.3555555000000005 055555500000000 If de- Catalyst,

lbs.

111114441111155511111555229.22555111114 4 4 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL depends on the theoretical molecular weight at the end of the initial oxyalkylation step; --i. e., oxyethylation for 1d through 16d, and oxypropylation for 17d through 32d.

It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included. 5 The data given in regard to the operating conditions is substantially the same as before and appears in Table i The products resulting from these procedures may con tain modest amounts, or have small amounts, of the 10 solvents as indicated by the figures in the tables. sired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what maybe termed an indifierent oxyalkylation,

i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; 7 or, one could use a combination in which butylene oxide is used along witheither one of the two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish to the caustic soda present.

.QOO.. 4 4 4 4 4446666666666666666 U. mmmmmwwwwwwwwsc%88888885555555511 1111 *Oxyelkylatloneusceptlble.

cmpd.

99%887779988876588888888QQQQQQQQ 1 34567 12346800000000033333333 1.1111111111111111 Molal ratio Ethyl. oxide to oxyto oxyalkyl. alkyl. suscept. suscept.

cmpd.

Sol. vent, lbs.

00000000000000005555555500000000 7 7 "AZ" T7 ZZZZZZZZTA iA ATmA mAJ I- TTTT-L Catalyst, lbs.

Table V Composition at end Propl. oxide, lbs.

Kerosene ,se4,7se

Ethl. oxide,

lbs.

Solubility Xylene Solvent, lbs.

00000000000000005565555500000000 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 4 AA iA mA AS TZZZZZ-L Catalyst, lbs.

Water Propl. oxide, lbs.

Time, hrs.

Ethl. oxide,

lbs.

Composition before O-Sd' mp lbs.

Oxyalkylation-susceptible.

Max. P p. s i.

39c. 39c. 39c. 39c.

Max. ti g Ex. No.

350.--. 6d 350-... 7d 350.... 8d- 350.... d..-.- 39c.... 10d

Ex. No.

kylation with'a monoepoxide'it is usually necessary to a .26 Table VIContinued Max. 1 'Max. Solubility ,Ex. temp pres., Time, .No. 0. p. s. 1. hrs.

Water 1 Xylene Kerosene do. Soluble.

Insouble. Insoluble. '0

PART16 used. Iffor any reason the reaction. does not proceed rapidly enough with the di'glycidyilether orother analor ous reactant then asmall amount offinely'divided causmedlate reactants are strongly basic. Initial oxyalkyla- 7 tion of these products with awmonoepoxide eordiepoxide {1c soda or sodium methylat? can be employed as a catacan be accomplished generally, at least in the initial stage, 3 3 amount general y employed would 1% without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylati'on .iem It goes wlthout saymg that the reactlon can take Place ploying monoepoxides in Part 5 immediately preceding. As a matter of fact, the procedure is substantially the same as using'a non-volatile monoepoxidesuch as-glycide or methylglycide. However, during progressive oxyal- The resin condensates which are employed -as intersusceptible. Generally speaking, this is most conveniently an aromatic solvent such as :xylene or a higher boiling coal'=tar:so1vent, or else-a similar high boiling V I aromatic solvent sobtained frompetrol'eum. 7 One can em- .ploy an oxygenated solvent such as the diethylether of :ethyleneglycol, or the diethylether o'f ,rpropyleneglycol, -.or similar ethers, either alone or in-conibination with a hydrocarbon solvent. The selection ,of the solvent depends in part on the subsequent use of the-derivatives :or reactionaproducts. Ifthe reaction products 'are to be .rendered solvent-"freeand it'iis necessary that the solvent clude alkaline materials, such as caustic'soda, caustic pot- :be y for example, by 0f ash, sodium methylate,:etc. Other catalysts may be acidic, dlstlllatlonl then Xylene j al'fimallc Petroleum in nature and are of the kind illustrated by iron and iSOlVent l iP llgl be3ubjected tin chloride. Furthermore, insoluble catalysts such as to oxyalky Subsequently, than the Boll/611i Shou clay or specially prepared mineral catalysts have been be one which is not oxyalkylation-susceptible. It is easy use a catalyst as previously described and, thus, there may or may not be suflicientcatalyst present for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was used.

Briefly stated then, employing polyepoxides in combination with a non-basic reactant the usual catalysts inin an inert solvent, i. e., one that is not oxyalkylation- 27 enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example 10 The product was obtained by reaction between diepoxide A and oxyalkylated resin condensate 10 which has been described in preceding Part and was obtained by the oxyalkylation of condensate 1b. The preparation of condensate 1b was described in Part 4, preceding. Details have been included in regard to both steps. Condensate lb, in turn, was obtained from diethanolamine and resin 2a; resin 2a, in turn was obtained from paratertiarybutylphenol and formaldehyde.

In any event, 223 grams of the oxyalkylated resin condensate previously identified as were dissolved in approximately an equal weight of xylene. About 2.25 grams of sodium methylate were added as a catalyst so the total amount of catalyst present, including residual catalyst from the prior oxyalkylation, was about 2.4 grams. 18.5 grams of diepoxide A were mixed with an equal weight of xylene. The initial addition of the diepoxide solution was made after raising the temperature of the reaction mass to about 105 C. The diepoxide was added slowly over a period of about one hour. During this time the temperature was allowed to rise to about 125 C. The mixture was allowed to reflux at about 135-140 C. using a phase-separating trap. A small amount of xylene was removed by means of a phase-separating trap so the refluxing temperature rose gradually to about 155 C. The mixture was refluxed at this temperature for about 3 /2 hours. At the end of this period the xylene which had been removed by means of the phase-separating trap was returned to the mixture. A small amount of material was withdrawn and the xylene 28 evaporated on a hot plate in order to examine the physical properties. The material was an amber, or light reddish amber, viscous liquid. It was insoluble in water; it was insoluble in gluconic acid, but it was soluble in xylene and particularly in a mixture of 80% xylene and methanol. However, if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend,

" or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone.

Generally speaking, the solubility of these derivatives 'is in line with expectations by merely examining the solubility of the preceding intermediates, to wit, the oxyalkylated resin condensates prior to treatment with the diepoxide. These materials, of course, vary from extremely water-soluble products due to substantial oxyethylation, to those which conversely are water-insoluble but xylene-soluble or even kerosene-soluble due to high stage oxypropylation. Reactions with diepoxides or polyepoxides of the kind herein described reduce the hydrophile properties and increase the hydrophobe properties, i. e.,.generally make the products more soluble in kerosene or a mixture of kerosene and xylene, or in xylene, but less soluble in water. Since this is a general rule which applies throughout, for sake of brevity future reference to solubility will be omitted.

The procedure employed, of course, is simple in light of what has been said previously and in effect is a procedure similar to that employed in the use of glycide or methylglycide as oxyalkylating agents. See, for example,

"j Part One of U. S. Patent No. 2,602,062 dated July 1,

1952, to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

Table VII Ex. Oxy Amt., Diep- Amt., Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (NaOCH lene, ratio reaction, temp., Color and physical state deusate used grs. grs. hrs. C.

223 A 18. 5 2. 4 242 2:1 3. 5 155 Reddish amber resinous mass. 375 A 18. 5 3. 9 394 2:1 3. 5 152 Do. 271 A 9. 3 2. 8 280 2:1 3. 5 148 D0 377 A 9. 3 3. 9 386 2:1 3. 5 150 Do 113 A 1. 9 1. 1 2:1 3. 4 160 Do 335 A 18. 5 3. 5 354 2:1 3 154 Do 375 A 18. 5 3. 9 394 2:1 4 155 Do 271 A 9. 3 2. 8 280 2:1 4 165 Do 314 A 9. 3 3. 2 323 2:1 4 D0 363 A 9. 3 3. 7 372 2:1 4 165 Do 391 A 18. 5 4. 1 409 2:1 4 160 D0 279 A 9. 3 2. 9 288 2:1 4 164 D0 363 A 9. 3 3. 7 372 2:1 4 Do 100 A 1. 9 1. 0 102 2:1 3. 5 D0 152 A 1.9 1. 5 154 2:1 4 165 D0 Table VIII Ex. Oxy. Amt, Die Amt, Catalyst Xy- Molar Time of Max. No. resin congrs. oxi e grs. (N aOCHz), lene, ratio reaction, temp., Color and physical state densate used grs. grs. hrs. O.

223 B 11 2. 3 234 2:1 4 Reddish amber resinous mass. 375 B 11 3. 9 386 2:1 4 155 Do. 271 B 5. 5 2. 8 277 221 4 152 D0 377 B 5. 5 3. 8 383 2:1 4 154 Do 113 B 1. 1 1.1 114 2:1 3. 5 154 Do 335 B 11 3. 5 346 2:1 4 150 D0 375 B 11 3. 9 386 2:1 4 Do 271 B 5. 5 2. 8 277 2:1 4 158 D0 314 B 5. 5 3. 2 320 221 4. 5 152 D0 363 B 5. 5 3.7 369 2:1 4. 5 160 Do 391 B 11 4. 0 402 2:1 4 158 Do 279 B 5. 5 2. 9 285 2:1 4 153 Do 363 B 5. 5 3. 7 369 2:1 4 155 Do 100 B 1. 1 1. 0 101 2:1 3 155 Do 152 B 1. 1 1. 5 153 2:1 4 158 Do Table IX Prob. mol. Ex. No. Oxyalkyl. weight. of Amount of Amount of resin conreaction product, grs. solvent densate product 4, 830 2, 415 1, 210 7, 870 3, 935 1, 970 11, 210 2, 240 l, 120 15, 440 3, 090 1, 540 20, 980 2, 298 l, 150 7, 070 3, 535 l, 770 7, 870 3, 935 1, 965 11,210 2, 240 1,120 12, 930 2, 385 1, 290 14, 880 2, 975 1, 490 8, 180 4, 090 2, 045 11, 530 2, 300 1,150 14, 880 2, 980 1,490 20, 370 2, 040 1, 020 30, 720 3, 070 535 Table X Prob. mol. Ex. No. .Oxyalkyl. weight of Amount of Amount of resin conreaction product, grs. solvent densate product At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or. the like. In some instances an oxygenated solvent, such as the diethylether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent, such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance, 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule actually may vary from the true molecular Weight by several percent.

The condensate can be depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CH (R,esin) CH (Amine) .If such product is subjected to oxyalkylation reaction involves the phenolic hydroxyls of the resin structure and, thus, can be depicted in the following manner:

(Amine) CH Oxyalkylated Resin) CH Amine) (Amine) CHz( Oxyalkylatcd Resin) CHz(Amin e) in which D. G. E. represents a diglycidyl ether as specified.

As has been pointed out previously, the condensation reaction may produce other products, including, for example, a product which may .be indicated thus .in light of Likewise, it is obvious that the two:different types of oxyalkylation-susceptible compounds may combine so-as to give molecules which may be indicated thus:

(LAmine)CHi(Oxya1kylated Resin) CHKAmine)I lArnine) CHKOxy'alkylated Resin) OHflAininei Oxyalkylated (Auilne) OH: (Amine) I J 0xyalkylated(Amine)CH:(Resin) Oxyalkylated (Amine) o ri -(Amine L l 'oxyalkylated (Amine) CHflAmine) PART '7 As to the use of conventional demulsifyingagents reference ismade ,to U. S. Patent No.. .2,626,929., dated January 7, 1943, to DeGroote, and particulary to Part Three. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is'made to Example 13b in said text beginning in column 1.5 and endingin column 18, reference should v,be to Example 3,e,.l1erein described.

31 PART 8 The products, compounds, or the like, herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the water-in-oil type as described in detail in Part 7, preceding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine one may employ what is a somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure IEHLN wherein R and R are alkyl groups.

It is not necessary to point out that, after reaction with a reactant of the kind described which introduces a basic nitrogen atom, the resultant product can be employed for the resolution of emulsions of the waterin-oil type described in Part 7 preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described in Part 6, preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boring or metalcutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; asdetergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type, as additives in the flotation of ores, and at times as aids in chemical reactions insofar that demulsification is produced between the insoluble reactants. Furvm aleic acid or anhydride, diglycolic acid, and various .tricarboxy and tetracarboxy acids so as to yield fieylated derivatives, particularly if one employs one mole of the polycarboxy acid for each reactive hydroxyl radical present in the final polyepoxide-treated product. Thus, one obtains a comparatively large molecule in which there is a plurality of carboxyl radicals. Such acidic fractional esters are suitable for the resolution of petroleum emulsions of the water-in-oil type as herein described.

Having thus described our invention what we claim as new and desire to secure by Letters Patent is:

i. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of producing a resin condensate by (A) condensing (a) an oxyalkylation-susceptiole, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (12) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to produce a monoepoxide oxyalkylated resin condensate; and then completing the reaction by a third step of (C) reacting said monoepoxide oxyalkylated resin condensate with nonaryl hydrophile polyepoxides containing at least two 1,2-epoxy rings and having two terminal 1,2-epoxy rings obtained by replacement of an oxygenlinked hydrogen atom in a water-soluble polyhydric alco hol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive monoepoxideoxyalkylated resin condensate and nonaryl polyepoxides be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction between the monoepoxide-oxyalkylated resin condensate and the nonaryl polyepoxide being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide.

2. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with'a-monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of producing a resin condensate by (A) condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde-resin having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde hav ing not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoam-ine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to produce a monoepoxide oxyalkylated resin condensate; and then completing the reaction by a third step of (C) reacting said monoepoxide oxyalkylated resin condensate with nonaryl hydrophile polyepoxides con taining at least two 1,2-epoxy rings and having two terminal 1,2-epoxy rings obtained by replacement of an oxygenlinked hydrogen atom in a water-soluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive monoepoxide-oxyalkylated resin condensate and nonaryl polyepoxides be members of the class consisting of non-thermosetting organic solventsoluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction between the monoepoxide-oxyalkylated resin condensate and the nonaryl polyepoxide being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide.

3. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and 3) oxyalkylation with a diepoxide; said first manufacturing step being a method of producing a resin condensate by (A) condensing (a) an oxyalkylation-susceptible, fusible. non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight correspondingto at least 3 and-not over 6 phenolic nuclei per resin molecule; said resin beir'igdifunctional only in regard to. methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being ofthe formula in which R is a saturated" aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoarnine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted ata temperature sufiiciently high to eliminate water and belowthe'pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation productresulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta alkylene oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to produce a monoepoxide oxyalkylated resin condensate; andrthen completing the reaction by a third step of (C) reacting said monoepoxide oxyalkylated resin condensate with nonaryl hydrophile diepoxides containing two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical H H H offw said diepoxide being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive monoepoxide-oxyal'kylated resin condensate and nonaryl diepoxides be members of the class consisting of non-thermosettin organic solvent soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of oxyalkylationand acylation-susceptible solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction between the monoepoxide-oxyalkylated resin condensate and the nonaryl diepoxide being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl diepoxide.

4. The process of claim 3 wherein the diepoxide contains at least one reactive hydroxyl radical.

5. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a diepoxide; said first manufacturing step being a method of producing a resin condensate by (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said rcsin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol;

in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to produce a monoepoxide oxyalkylated resin condensate; and then completing the reaction by a third step of (C) reacting said monoepoxide oxyalkylated resin condensate with a 'hydroxylated diepoxypolyglycerol containing two terminal 1,2-epoxy rings and having not more than 20 carbon atoms; with the further proviso that said monoepoxide-oxyalkylated resin condensate and said hydroxylated diepoxyglycerol be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with theadded proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; said reaction between the monoepoxide-oxyalkylated resin condensate and the hydroxylated diepoxypolyglycerol being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the hydroxylated diepoxyglycerol.

. 6. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei.

7. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei and the difunctional monohydric phenol employed in forming the initial phenol-aldehyde resin is para-substituted.

8. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei, and the difunctional monohydric phenol employed in forming the initial phenol-aldehyde resin is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group.

9. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei, and the difunctional monohydric phenol employed in forming the initial phenol-aldehyde resin is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the aldehyde employed in forming the initial phenol-aldehyde resin is formaldehyde.

10. The method of claim 5 wherein the hydroxylated diepoxypolyglycerol has not over 5 glycerol nuclei, and the difunctional monohydric phenol employed in forming the initial phenol-aldehyde resin is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the aldehyde employed in forming the initial phenol-aldehyde resin is formaldehyde, and the total number of phenolic nuclei in the initial resin are not over 5.

11. The product obtained by the method described in claim 1.

12. The product obtained by the method described in claim 10.

No references cited. 

1. A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEOPXIDE AND (3) OCYALKYLATION WITH A POLYEPOXIDE; SAID FIRST MANUFACTURING STEP BEING A METHOD OF PRODUCTING A RESIN CONDENSATE BY (A) CONDENSING (A) AN OXYALKYLATION SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-SOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN ANERAGE MOLECULAR WEIGHT COMPESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECILE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON AND REACTIVE TOWARD SAID PHENOL; SAID RESIN FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 